Negative emotion differentiation facilitates emotion regulation. However, whether individual differences in negative emotion differentiation is associated with resting-state spontaneous emotion regulation remains unclear. This study aimed to explore the effect of individual differences in negative emotion differentiation on spontaneous emotional regulatory processes as indexed by resting electroencephalogram (EEG) indicators (e.g., frontal alpha asymmetry and theta/beta ratio). Participants (n = 40, M = 21.74 years, 62% women) completed a negative emotion differentiation task. Afterward, 4 min of resting EEG data were recorded. Multiple regression results showed that negative emotion differentiation significantly predicted the alpha asymmetry at electrode pairs (F4–F3 and FP2–FP1) and the theta/beta ratio at the F3 and FZ electrode sites. Individuals with high negative emotion differentiation presented more left-lateralized activations and a lower theta/beta ratio. Taken together, these results suggest that individuals with high negative emotion differentiation show enhanced spontaneous emotional regulatory functioning. Thus, we provided the first resting-state neural evidence on emotion differentiation of spontaneous emotional regulatory functioning.